1. Field of the Invention
The present invention relates to olefin metathesis. More particularly, the present invention relates to synthesis of olefin metathesis catalysts.
2. General Background of the Invention
The advent of well-defined, highly reactive catalysts for olefin metathesis (ring-closing metathesis, RCM; ring-opening metathesis polymerization, ROMP; cross metathesis, CM; and their combinations) has made this technique a powerful tool in organic synthesis and polymer chemistry.1 Metal-carbene complexes of the type (PCy3)2Ru(═C(H)Ph)Cl2 (1)2, and its analogues modified with nucleophilic carbenes (PCy3)Ru(IMes)(═C(H)Ph)Cl23 (2), and (PCy3)Ru(SIMes)(═C(H)Ph)Cl2 (3)4 where IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene and SIMes=1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, are highly efficient catalyst precursors. The inventor and his colleagues have shown that the complexes of unsaturated “Cα” ligands other than the alkylidenes such as (PCy3)2Ru(3-phenylindenylid-1-ene)Cl2 (4) and (PCy3)(IMes)Ru(3-phenylindenylid-1-ene)Cl2 (5) are also active catalyst precursors in the ring-closing metathesis of dienes (FIG. 1).5
In its most widely used preparation, complex 1 has been synthesized by reaction of RuCl2(PPh3)3 with diazo compound according to eq. 1.
Complexes 4 and 5 are of particular interest since they are easily synthesized from RuCl2(PPh3)3 and an alkyn-ol followed by simple ligand substitution reactions according to eq. 2.
This unusual rearrangement of an alkyn-ol into an indenylidene results in ruthenium complexes that are quite active in a number of olefin metathesis transformations.
The following US patents are incorporated herein by reference:    U.S. Pat. No. 6,403,802 Use of catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in amination reactions    U.S. Pat. No. 6,403,801 Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene of imidazolidine-2-ylidene in Suzuki coupling reactions    U.S. Pat. No. 6,369,265 Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in Kumada coupling reactions    U.S. Pat. No. 6,362,357 Use a catalyst system comprising nickel palladium or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in stille coupling reactions    U.S. Pat. No. 6,316,380 Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene.    U.S. Pat. No. 6,586,599 Catalyzed coupling reactions of aryl halides with silanes;    U.S. Pat. No. 6,583,307 Convenient and efficient Suzuki-Miyaura cross-coupling catalyzed by a palladium/diazabutadiene system;    U.S. Pat. No. 6,403,802 Use of catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in amination reactions;    U.S. Pat. No. 6,403,801 Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene of imidazolidine-2-ylidene in suzuki coupling reactions;    U.S. Pat. No. 6,369,265 Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in kumada coupling reactions;    U.S. Pat. No. 6,362,357 Use a catalyst system comprising nickel palladium or platinum and imidazoline-2-ylidene or imidazolidine-2-ylidene in stille coupling reactions;    U.S. Pat. No. 6,316,380 Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene;    U.S. Pat. No. 5,110,948 Organosamarium catalysts for the hydroamination of olefins;    US Patent Application 20020198423 A1 Convenient and efficient suzuki-miyaura cross-coupling catalyzed by a palladium/diazabutadiene system;    United States Patent Application 20020173650 A1 Metal complexes for hydrogenation of unsaturated compounds;
All of my prior US patent applications are incorporated herein by reference, including Ser. Nos. 09/392,869, 09/507,958, 09/907,526, 10/011,680 (application published as US2002/0173650), No. 60/407,073.